Light-sensitive silver halide color-photographic material

ABSTRACT

Light-sensitive silver halide color-photographic material comprises a support and, coated thereon, a light-sensitive silver halide emulsion layer containing a color former, and a complex formed from (a) an alkali-soluble phenolic compound having a hydroxyl group on its benzene nucleus and capable of reducing silver halide and (b) a water-soluble polymeric vinyl compound capable of forming a complex with said phenolic compound, said complex being included in said emulsion and/or in a layer contiguous therewith.

United States Patent [72] Inventors Masanobu Oguchi; v

Akira l-lorikoshi; Kensaku Tanimura, all of Tokyo, Japan [21] Appl. No.709,174 [22] Filed Feb. 29, 1968 [45] Patented Oct. 26, 1971 [73]Assignee Konishiroku Photo Industry Co., Ltd.

Tokyo, Japan [3 2] Priority Mar. 3, 1967 [3 3] Japan [31] 42/131,111

[54] LIGHT-SENSITIVE SILVER HALIDE COLOR- PHOTOGRAPHIC MATERIAL 5Claims, No Drawings [52] US. Cl 96/77, 96/100, 96/114 [51] Int. Cl G03c1/42 [50] Field ofSearch 96/1 14,95, 96, 77, 100

Primary Examiner-Ronald H. Smith Attorney-Amold Robinson ABSTRACT:Light-sensitive silver halide color-photographic material comprises asupport and, coated thereon, a light-sensitive silver halide emulsionlayer containing a color former, and a complex formed from (a) analkali-soluble phenolic compound having a hydroxyl group on its benzenenucleus and capable of reducing silver halide and (b) a water-solublepolymeric vinyl compound capable of forming a complex with said phenoliccompound, said complex being included in said emulsion and/or in a layercontiguous therewith.

developer in its oxide form. Since conversion of the color developerinto its oxide form occurs by the treatment of a latent silver image(silver ion) ion) with a developing solution containing said colordeveloper, the formation of dye is somewhat restricted to around thereduced silver particles, thereby to cause graininess of the dye.

Various methods have been proposed heretofore to obtain improvedgraininess. For example, it is a common practice to use silver halide inthe form of particles as fine as possible. However, this usually sufferfrom decrease in photographic sensitivity. In some instance, use of acolor former having delayed coupling rate or a protected oil-solublecolor former having a low rate of reaction with the oxide of a colordeveloper is proposed thereby to have sufficient diffusion of the oxidewith the less degradation of graininess. However, this method isdisadvantageous because it makes difficult silver development to proceedand results in decrease in photographic speed and gradient. Use of ablack-and-white developer and a color developer in a developing solutionis also known to obtain their superadditive effect for colordevelopment. However, this procedure makes the maintenance of adeveloping bath considerably troublesome. lncorporation of ablack-and-white developer in a light-sensitive layer is notrecommendable because this causes undesired migration of said agent intoother photographic layers. Further, said agent is likely to be dissolvedout from the layer during development.

Accordingly, it is an object of the invention to provide alight-sensitive silver halide color-photographic material with improvedgraininess and free from color fog.

The above-mentioned object can be accomplished by the present invention.In accordance with the present invention, there is provided alight-sensitive silver halide color-photographic material whichcomprises a support and, coated thereon, a light-sensitive silver halideemulsion layer containing a color former, characterized by that thecombination of (a) an alkali-soluble phenolic compound having a hydroxylgroup on its benzene nucleus and capable of reducing silver halide and(b) an water-soluble polymeric vinyl compound capable of forming acomplex with said phenolic compound exists in a light-sensitive silverhalide emulsion layer and/or the layer contiguous therewith.

For the purpose of the present invention, it is essential to incorporatethe combination of both of the phenolic compound (a) with the polymericvinyl compound (b) into a light-sensitive silver halide emulsion layerand/or the layer contiguous therewith. It is presumed, without fullexactness, that the above-referred combination of the phenolic compound(a) with the polymeric vinyl compound (b) is present in the form of acomplex of the compounds (a) and (b), as such complex is understood asthe result of the formation of a hydrogen bond between the hydroxylgroup of the phenolic compound and the oxygen atom of the heterocyclicketo group of the polymeric vinyl compound when both of these compoundsare brought into an aqueous or alcoholic medium. As well known for thoseskilled in the art, the present application is applicable tolight-sensitive silver halide color-photographic films includingmonochromatic color films and tri-color films. Therefore, thecombination of the compounds (a) and (b) can be incorporated in one ormore light-sensitive silver halide emulsion layers. Similarly, it can beincorporated in other photographic layers contiguous to thelight-sensitive emulsion layers, said other photographic layers beinginter layer, protective layer, antihalation layer, subbing layer, andfilter layer.

The essential requirements for the phenolic compound (a) outlined beforeare that it is soluble in alkali; it has on its benzene nucleus at leastone hydroxyl group which serves to form a hydrogen bond; and it iscapable of reducing silver halide to silver. Suitable phenolic compounds(a) as referred to may be obtained from a wide variety of conventionallyknown black-and-white developers. Hydroquinone, aminophenol andpyrogallol which are well known black-and-white developers are typicalphenolic compounds useful in this invention. Nucleically substitutedhydroquinones and N-substituted aminophenols are also useful. Thefollowing are typically suitable compounds for the purpose of thisinvention.

I HOG-0H Hydroqulnone HO OH Tert. butylhydroqulnone 0: 1 (tert.)

(III) HO -OH Acetoxyhydroquinone HO OH Ethoxycarbonylhydroqulnone (V)CHzNHCiHlOH 2, 5-dl-(ethanolamtnometh 1 HO OH hydroquinones yHOHACzHNHzC (VI) H0 HO -O 0 O 01H; Sym. ethoxycarbonyl-pyrogallol (VII)H0 NH: D'Amlnophenol (VIII) H0 NHCH;SO;H p-Sullomethylaminophenol o-(3,4-Methy1enedioxybenzalamIno)-phenol H0 N=CH p-Benzalamlnophenol HO N=CHOl p-(p-Chlorobenzalamtno)- phenol H0 N=CHO on,p-(p-Methoxybenzalandno)- phenol Almost all of the conventionally knownblack-and-white developers are usable in this invention, as far as saiddevelopers have a hydroxyl group to form a hydrogen bond. In thefollowing description, therefore, the term black-andwhite developer maybe interpreted synonymous with the term Phenolic compound (a)" asreferred to above.

Suitable water-soluble polymeric vinyl compounds (b) are thosecontaining the recurrent monomeric unit of the general formula wherein Ameans an atomic grouping necessary to constitute, together with theadjacent nitrogen and carbon atoms, a fiveto seven-membered ring. Thesepolymeric vinyl compounds can be prepared by the homopolymerization orcopolymerization of an appropriate monomer corresponding to the saidgeneral formula. Typically useable polymeric vinyl compounds (b)include, for instance, polyvinyl pyrrolidone, polyvinyl oxazolidone,polyvinyl piperidone, polyvinyl caprolactam, etc. If desired, thesecompounds may be modified by the introduction of any suitablesubstituent, e.g. a solubilizing group, so as to impart desired usefulproperty to said compounds. The essential requirement for the polymericvinyl com-pounds (b) is that they are soluble in water and capable ofcomplexing with the above-mentioned phenolic compounds (a) (or theblack-and-white developers) of the pH range of about 6.0 to about 8.0.Preferably, these polymeric vinyl compounds should have an averagemolecular weight as great as about 10,000 or more. If these polymershave too small molecular weight, the resulting combination products orcomplexes still tend to migrate in photographic layers or inducedissolution of color formers or dyes in developing solutions duringcolor development. It is desirable that the polymeric vinyl compound canproduce a complex having a sufficiently great molecular weight toprevent its migration in photographic layers.

The ratio of these polymers with the black-and-white developer to becombined may be defined as mm 2:1- l:l, wherein m means thepolymerization degree of the polymer and n is the mole number of theblack-and-white developer. Depending on the types of the polymer andblackand-white developer, the higher or lower ratio (m/n) may be used.The black-and-white developer may be used singly or in combination toform one or more complexes.

The polymer and the black-and-white developer may be added separately toa coating liquid to form a complex in situ. Alternatively, a complex isformed in water or alcohol by the reaction of the polymer with theblack-and-white developer and then added to a photographic coatingliquid. The amount used may be 1-30 percent based on the amount of afilmforming binder such as gelatine, but this can be varied depending onthe type of the complex, the silver halide content of the emulsionlayer, the silver content of the filter layer, the hardness of thebinder layer, etc. X

This invention is applicable to any light-sensitive silver halidecolor-photographic material containing a color former which may bealkali-soluble coupler having a nondiffuse group, oil-solubleincorporated coupler, etc. or colorless coupler, colored coupler, etc.Similarly, any color developer which is conventionally known is alsousable for color development of the color-photographic material of thisinvention.

As explained hereinabove, the present invention can exhibit thesuperadditive effect of the color developer and the blackand-whitedeveloper in Redox system during color development, thereby to obtainimproved graininess of dyes and decrease of fogging, without sacrificingphotographic speed and gradient.

The following examples describe certain ways in which the principle ofthe invention has been applied, but are not to be construed as limitingits scope.

EXAMPLE 1- A high speed green-sensitive photographic emulsion isprepared which contains 100 g. of gelatin and 0.35 moles of silverbromoiodide containing 5 mole percent silver iodide. This emulsion isdivided to 12 equal portions. Six portions are added with each one ofthe before-indicated phenolic compounds (II), (IV), (VI), (VIII) and (X)and poly-N-vinyl-2- pyrrolidon e having an average molecular weight of350,000 (this is referred to as the compound (P), hereinafter). Fiveportions are added with each one of the compounds (II), (IV), (VIII) and(X), respectively, combined with the compound (P) in methanolicsolution. The remaining one portion is used as a control sample byadding thereto methanol only. Each of these emulsions are added with amagenta color former, l-[4- 4-tert.butylphenoxy)-3-sulfophenyl -3(3-palmitamidobenzamido)-5-pyrazolone, in the proportion of 3 molepercent based on the molar content of the silver halide and thenadjusted at pH 6.8. These emulsions are coated on cellulose triacetatefilm based and dried. The resulting film strips are subjected toexposure to light in a scnsitometer. After the light exposure, thesefilm strips are treated at 20 C. for 10 minute with a developingsolution of the following formulation.

4-Amino-N-ethyl-N-[ B-methanesulfonamidoelhyl| Water to make up I I.

After development, the film strips are washed with water. for 5 secondsand treated with a magnesium sulfate solution at 20 C. for 10 minutes.Then, they are rinsed, bleached, rinsed, fixed, rinsed and dried in themanner known per se.

Complementary color density of the color-developed film strips ismeasured. Fog, relative speed at the density of 0.l above fog., gammavalue averaging those of from the point at which the photographic speedis obtained to the point at which an exposure amount as much as 10 timesis given are obtained. The color-developed film negatives thus obtainedare printed by enlargement (x10) on Sakura color photographic paper.These color prints are visually compared with the control color print byl0 persons with reference to a series of standard color image sampleswhich represent l0 discriminating grades of graininess. Rating ofgraininess of the tested color prints is determined. For example, +2means that the color print in question is better in graininess by twogrades than the control color print. The results are set forth in table1, wherein the amount is expressed by percent weight based on thegelatine amount. The complex is expressed as by [Plm [II] n, wherein mand n are the molar ratio of the individual components.

TABIJE 1 Photographic Film strip properltes Dlfier ence of Relagrade inAmount tive Garngraini- Compound percent Fog speed ma ness Control 0. 20100 0. 65 [g] 10 0. 18 0. 63 +2 1.50 0. 17 0.67 l 1.64 0.19 0.65 0 [VI8.56 0.22 95 0.64 +1 [VI 1]. 3.66 0. 18 95 0.63 +1 [X] 0.25 0. 16 960.62 +2 [P] 10[II] (10) (1. 50) 0. 15 100 0. 63 +5 [P] 10 [IV] 1 (10)(1.64) 0. 13 98 0.66 +6 [P] 5W1] 1 (10) (3. 56) 0. 14 96 0. 67 +4 [P5[VIII[1. (10) (3.66) 0.18 110 0.64 +4 [P] 70[X] 1 (10 (0. 25) 0. 17 0.62 +7 can show remarkably improved graininess of dyes without decreasein photographic speed and gradient, in comparison with the control, thepolymer alone and the black-and-white developer alone. cEXAMPLE 2 A highspeed red-sensitive photographic emulsion is prepared which contains 80g. of gelatine and 0.35 moles of silver bromoiodide containing 4 molepercent silver iodide. The emulsion thus prepared is divided to sixequal portions, one of which is used as a control emulsion and theremaining five are added with each one of the compound (Ill), poly-N-vinyl-5-methyl-2-oxazolidinone having an average molecular weight of250,000 (this is referred to as the compound [0] hereinafter), copolymerof poly-N-vinyl-2-pyrrolidone having an average molecular weight of160,000 with sodium polymethacrylate having an average molecular weightof 32,000 (this copolymer is referred to as the compound (PM)hereinafter), a complex of (III) with (0) and a complex of III) with(PM). The thus prepared emulsions are added with a cyan color former,l-hydroxy-2-naphthoyl-N-octadecylamido-4-sulfonic acid, in the amount of6 mole percent based on the silver halide content. The emulsions areadjusted pH 6.8. These are coated on cellulose triacetate film bases anddried. The each samples obtained are exposed to light in a sensitometer.The same measurement as in example 1 is conducted. The results are setforth in table 2.

As apparent from table 2, use of the complexes according to theinvention is effective to improve graininess of dyes and decrease fog,without any adverse influence on photographic speed and gamma.

EXAMPLE 3 A colloidal silver suspension containing 100 g. of gelatineand 5.2 g. of blue colloidal silver is prepared. This suspension is foruse in the preparation of antihalation layer. This is divided to fiveequal portions, one of which is used as a sample and the remaining fourare added with each of the compound (IV), the compound (XII),poly-N-vinyl-Z-pyrrolidone having an average molecular weight of 350,000(this is referred to (P), hereinafter), the complex of (IV) with (P) andthe complex of (XII) with (P). The emulsions are adjusted at pH 6.8 andthen coated on cellulose triacetate film bases. The high speedred-sensitive color photographic emulsion containing a cyan color fonnerwhich emulsion is used in example 2 is overcoated and dried. Each filmsamples thus prepared are exposed to light in a sensitometer and thentreated with a developing solution of the following formulation:

N,N-diethyl-p-phenylenediamine monohydrochloride 2.5 g. Anhydrous sodiumsulfite 4 g. Sodium carbonate monohydrate 50 g. Hydroxylaminesemi-sulfate 0.6 g. Potassium bromide 2 Water to make up I I.

After development, these film samples are worked up in the same manneras in example I. The results of measurement are set forth in table 3. Itis to be noted that the control (I) appearing in table 1 is the same asthe control of example 2 and has no antihalation layer, and the control(II) is the control sample with antihalation layer.

TABLE 3 Photographic Film strip properties Dlfieronce of Relagrade inAmount tive Gamgraini- Compound (percent) Fog speed maness [I] 0.16 940.67 0 [II] 0.28 100 0.68 P] 15. 0. 21 102 0. 67 0 [IV] plus lXII]..(2.46) (0.45) 0.25 0.68 +1 [P2150 [IV] 7 As apparent from table 3, thepresent invention is useful to improve graininess remarkably anddecrease fog, without any adverse influence on photographic speed andgamma.

What we claim is:

I. A light-sensitive silver halide color-photographic material whichcomprises a support and, coated thereon, a light-sensitive silver halideemulsion layer containing a color coupler, characterized in this thatthe combination of an alkali-soluble phenolic compound having at leastone hydroxyl group on its benzene nucleus and capable of reducing silverhalide with a water-soluble polymeric vinyl compound containing therecurrent unit of the general formula wherein A means an atomic groupingnecessary to constitute, together with the adjacent nitrogen and carbonatoms, a fiveto seven-membered oxygen-containing heterocyclic ring, andcapable of forming a complex with said phenolic compound through ahydrogen bond, is present in said light-sensitive silver halide emulsionlayer and/or the layer contiguous therewith.

2. A light-sensitive silver halide color-photographic material asclaimed in claim I, wherein said material is a monochromatic color ortri-color photographic film.

3. A light-sensitive silver halide color-photographic material asclaimed in claim 1, wherein said combination is present in at least onelayer selected from light-sensitive emulsion layer, interlayer,protective layer, antihalation layer, filter layer and sublayer.

4. A light-sensitive silver halide color-photographic material asclaimed in claim I, wherein said phenolic compound is one memberselected from black-and-white developers having at least one phenolichydroxyl group.

5. A light-sensitive silver halide color-photographic material asclaimed in claim I, wherein said polymeric vinyl compound is one memberselected from polyvinyl pyrrolidone, polyvinyl oxazolidone, polyvinylpiperidone and polyvinyl caprolactam.

a: s: t e

2. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said material is a monochromatic color or tri-color photographic film.
 3. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said combination is present in at least one layer selected from light-sensitive emulsion layer, interlayer, protective layer, antihalation layer, filter layer and sublayer.
 4. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said phenolic compound is one member selected from black-and-white developers having at least one phenolic hydroxyl group.
 5. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said polymeric vinyl compound is one member selected from polyvinyl pyrrolidone, polyvinyl oxazolidone, polyvinyl piperidone and polyvinyl caprolactam. 